4-oxatricyclo[5.2.1.0^2,6]dec-8-en-10-one | 122601-57-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: 4-oxatricyclo[5.2.1.0^2,6]dec-8-en-10-one
• 英文别名: (1R,2R,6S,7S)-4-oxatricyclo[5.2.1.02,6]dec-8-en-10-one
• CAS: 122601-57-4
• 化学式: C₉H₁₀O₂
• 分子量: 150.177
• InChiKey: NRULWYOBTDVMGG-SOSBWXJGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-oxatricyclo[5.2.1.0^2,6]dec-8-en-10-one 在 sodium hydroxide 、 nicotinamide adenine dinucleotide phosphate (NADP⁺) 、 聚甘氨酸 作用下， 以74%的产率得到(1S,2S,6S,7R)-4,8-Dioxa-tricyclo[5.2.2.0^2,6]undec-10-en-9-one
  参考文献：
  名称：

  The enzymatic Baeyer–Villiger oxidation of a series of bicyclo[2.2.1]hept-2-en-7-ones

  摘要：

  利用从 Acinetobacter NCIB 9871 细菌中分离出的环己酮加氧酶（E.C. 1.14.13.-），对一系列双环[2.2.1]庚-2-烯-7-酮进行 BaeyerâVilliger 氧化反应，可得到对映体过量的内酯产品。

  DOI：

  10.1039/c39920001384
• 作为产物：
  描述：

  5,5-二甲氧基-1,2,3,4-四氯环戊二烯 在 吡啶 、 lithium aluminium tetrahydride 、 氨 、 sodium 、 对甲苯磺酸 、 对甲苯磺酰氯 作用下， 以 四氢呋喃 、 丙酮 、 xylene 为溶剂， 反应 26.0h， 生成 4-oxatricyclo[5.2.1.0^2,6]dec-8-en-10-one
  参考文献：
  名称：

  4-Oxatricyclo[5.2.1.0^2,6]decan-10-one and 4-Oxatricyclo[5.2.1.0^2,6]dec-8-en-10-one. Experimental and DFT Investigations of the π-Selectivities

  摘要：

  Ab initio MO and experimental pi-selectivities of hydride additions to 4-oxatricyclo[5.2.1.0(2.6)]decan-10-one and 4-oxatricyclo[5.2.1.0(2.6)]dec-8-en-10-one are described. The interactions Of sigma(C1-C2) and sigma(C6-C7) with pi*(C=O), on one hand, and those of sigma(C1-C9) and sigma(C7-C8) with pi*(C=O), on the other hand, support anti-selectivities for both. This is in full accordance with the experiments. The arguments that are based on electrostatic interactions and electron donation from the ring oxygen do not apply.

  DOI：

  10.1021/jo015945t

文献信息

• Palladium-Catalyzed Arylative Ring-Opening Reactions of Norbornenols: Entry to Highly Substituted Cyclohexenes, Quinolines, and Tetrahydroquinolines
  作者：Michael Waibel、Nicolai Cramer

  DOI：10.1002/anie.201001752

  日期：2010.6.14

  retro‐allylations from norbornene‐derived tertiary alcohols participate in coupling reactions with aryl‐ or vinylhalides to provide tetrasubstituted cyclohexenes with excellent regio‐ and diastereoselectivity (see scheme). This procedure was also exploited in domino reactions to access highly functionalized quinolines and tetrahydroquinolines.

  逆转：降冰片烯衍生的叔醇的钯催化逆烯丙基化参与与芳基卤化物或乙烯基卤化物的偶合反应，从而提供具有出色的区域和非对映选择性的四取代环己烯（参见方案）。在多米诺反应中也采用了该程序来获得高度官能化的喹啉和四氢喹啉。
• Desymmetrizations of meso-tert-norbornenols by rhodium(<scp>i</scp>)-catalyzed enantioselective retro-allylations
  作者：Michael Waibel、Nicolai Cramer

  DOI：10.1039/c0cc01950j

  日期：——

  Rhodium-catalyzed desymmetrizations of meso-tert-norbornenols by retro-allylations generate allyl-rhodium species that allow for a rich and diverse downstream reactivity.

  在铑催化下，介-叔-降冰片烯醇通过逆烯丙基化反应发生脱对称反应，生成烯丙基铑物种，从而实现丰富多样的下游反应。
• π-Facial selectivities in nucleophilic additions to 4-hetero-tricyclo[5.2.1.02,6]decan-10-ones and 4-hetero-tricyclo[5.2.1.02,6]dec-8-en-10-ones: an experimental and computational study
  作者：Goverdhan Mehta、Vanessa Gagliardini、U.Deva Priyakumar、G.Narahari Sastry

  DOI：10.1016/s0040-4039(02)00320-9

  日期：2002.4

  Several endo-tricyclo[5.2.1.02,6]decan-10-ones and endo-tricyclo[5.2.1.02,6]dec-8-en-10-ones with hetero atom modifications at the distal C-4 position have been subjected to hydride reduction. π-Face selectivities in these systems are largely governed by the same electronic factors that were earlier identified in the case of the norbornyl system. A computational study demonstrates good predictability

  在远端C-4位置具有杂原子修饰的几个内-三环[5.2.1.0 2,6 ] decan-10- one和内-三环[5.2.1.0 2,6 ] dec-8-en-10-one具有进行氢化物还原。这些系统中的π-表面选择性在很大程度上受先前在降冰片烯系统中所确定的相同电子因素的支配。一项计算研究表明，在半经验水平上具有良好的可预测性。
• Absence of Heteroatom Kinetic Effects in p-Route to Carbocations
  作者：Alex Nickon、Stella S. Jones、Billy J. Parkhill

  DOI：10.3987/com-88-s100

  日期：——
• 4-Oxatricyclo[5.2.1.0^2,6]decan-10-one and 4-Oxatricyclo[5.2.1.0^2,6]dec-8-en-10-one. Experimental and DFT Investigations of the π-Selectivities
  作者：Veejendra K. Yadav、Rengarajan Balamurugan

  DOI：10.1021/jo015945t

  日期：2002.1.1

  Ab initio MO and experimental pi-selectivities of hydride additions to 4-oxatricyclo[5.2.1.0(2.6)]decan-10-one and 4-oxatricyclo[5.2.1.0(2.6)]dec-8-en-10-one are described. The interactions Of sigma(C1-C2) and sigma(C6-C7) with pi*(C=O), on one hand, and those of sigma(C1-C9) and sigma(C7-C8) with pi*(C=O), on the other hand, support anti-selectivities for both. This is in full accordance with the experiments. The arguments that are based on electrostatic interactions and electron donation from the ring oxygen do not apply.